Polyhexahydrotriazine dielectrics

ABSTRACT

Low dielectric constant (low-k) polyhemiaminal (PHA) and polyhexahydrotriazine (PHT) materials with cyclic aliphatic ring structures are described. The materials are formed by a method that includes heating a mixture comprising amines and paraformaldehyde. The reaction mixtures may be used to form low-k PHT prepregs, composites and dielectrics used in integrated circuits.

FIELD

The present invention relates to improving the physical and electricalproperties of polyhexahydrotriazine (PHT) polymers and networks, andmore specifically to new low dielectric constant (low-k)polyhexahydrotriazines (PHTs) for application in the field ofelectronics.

BACKGROUND

As device dimensions decrease and device densities increase, chipperformance degrades due to signal delays and cross talk between theconductor lines. Signal propagation delays are characterized by theproduct of metal resistance (R) times the capacitance (C) of the lines(RC delay), which has the dimension of time in seconds. The RC delaydepends on the resistivity of the wiring metallurgy, the dielectricconstant(s) of the insulating media, and the dimensions andconfiguration of the metal lines. The relatively recent change inmetallurgy from aluminum to copper has reduced the resistivity of themetal by about 30%, providing a significant improvement in performance.However, the RC delay phenomenon is exacerbated by the highpolarizability of conventionally integrated SiO₂ (k˜4) dielectric andthe need to keep conductor lines as short as possible. While the switchto copper metallurgy and new multilevel wiring schemes have amelioratedthe RC delay problem, as feature sizes go below 0.25 μm, this alone willnot provide a solution.

The use of an insulator with a dielectric constant (k) lower than SiO₂would reduce parasitic capacitance and crosstalk, but it must still meeta number of stringent integration requirements including: thermalstability ≧400° C., resistance to crack generation and propagation, lowdefect density, low water uptake, chemical resistance, processability byphotolithographic techniques and gas-phase etching, as well as acapacity for chemical mechanical planarization (CMP). Inorganicinsulators may satisfy most of these requirements, however,extendibility to future device generations requires the introduction ofporosity (e.g., k=1 for air) to lower the dielectric constant.

Porous low-k materials have been introduced for use in specialty ICsover the last several years. The porous materials exhibit dielectricconstants from about 2.5 to about 3.0, but unfortunately exhibitlow-moduli, are prone to cracking, and mostly contain interconnectedpores, which makes subsequent processing steps such as electroplatingand CMP more difficult. Because of these drawbacks, there is a need forfully dense materials, such as low-k PHTs, with improved properties thatdo not suffer from the disadvantages of porous low-k materials in ICapplications.

New generation printed circuit boards (PCBs) used in high speed (>2Gb/s) telecommunication equipment and internet infrastructure serversface a similar challenge as ICs due to decreasing device and substratedimensions. PCBs increasingly put more function in a smaller space,which requires more components, while utilizing smaller bond pads,smaller lines and tighter pitch. The shrinking form factors combinedwith the future integration of optical signal transmission in 3Dpackaging schemes has driven the need for lower dielectric constantprinted circuit board substrates. Because of the new PCB challenges, itwould be an advantage to replace high k epoxy matrix resins used in PCBs(e.g., FR-4 type), with new low-K PHTs to reduce crosstalk and parasiticcapacitance.

SUMMARY

Low-k PHA and PHT materials with cyclic aliphatic ring structures aredescribed. The materials are formed by a method that includes heating amixture comprising amines and paraformaldehyde. The reaction mixturesmay be used to form low-k PHT prepregs, composites and dielectrics usedin integrated circuits. Specifically, embodiments of the disclosureinclude a PHT comprising a plurality of trivalent hexahydrotriazinegroups having the structure

and a plurality of carbon groups having the structure

andwherein each wavy bond site of a given hexahydrotriazine group iscovalently linked at a respective wavy bond site of a carbon group, andeach wavy bond site of a given carbon group is covalently linked at arespective wavy bond site of a hexahydrotriazine group, and wherein atleast one of 1, 2, and 3 comprises a chemical group that is a cycliccarbon chemical group, or 1 and 2 can be part of an cyclic carbonchemical group, or 2 and 3 can be part of an cyclic carbon chemicalgroup, or 1 and 3 can be part of an cyclic carbon chemical group. PHTsherein are described wherein at least one of 1, 2, and 3 is a covalentlybonded carbon substituent, and wherein at least one of 1, 2, and 3comprises a covalently bonded cyclic aliphatic chemical group, andwherein at least one cyclic aliphatic chemical group comprises at leastone cyclic carbon ring, and more specifically, wherein at least onecyclic carbon ring is fused to at least one other cyclic carbon ring.Also described are PHTs wherein at least one of 1, 2, and 3 covalentlybonds at least one hexahydrotriazine group to another hexahydrotriazinegroup. The PHTs of the disclosure may further comprise at least 50% bymole aliphatic carbon-carbon chemical bonds based on polymer, andcomprising at least 50% by mole cyclic aliphatic carbon-carbon chemicalbonds based on polymer. PHTs of the disclosure are also describedcomprising less than 50% by mole aromatic carbon-carbon chemical bondsbased on polymer. In some embodiments, PHTs comprising covalently bondedfluorine atoms, cyclic chemical groups that contain covalently bondedfluorine atoms are described. The PHTs of the disclosure exhibit adielectric constant that is less than 5, and a dielectric constant thatis at least 1.8. Embodiments of the disclosure elucidate a method ofproducing a composite article, comprising: forming a mixture comprisinga solvent, amines, and paraformaldehyde, and; heating the mixture to afirst temperature to produce a first partially cured mixture of a firstviscosity; coating a work piece with the first partially cured mixtureof the first viscosity to produce polymer impregnated fibers (prepreg);heating the prepreg to a second temperature to produce a B-stage prepregof a second viscosity; cooling the B-stage prepreg; forming an articlefrom the B-stage prepreg; and heating the article at a temperature fromabout 150° C. to about 280° C. to form a fully cured compositecontaining polyhexahydrotriazine. In some embodiments of the method, theamines of the mixture comprise at least 50% by mole cyclic aliphaticamine based on polymer and the amines of the mixture comprise of lessthan 50% by mole aromatic amine based on polymer. The method furtherdescribes a first partially cured mixture of the first viscosity isproduced at a temperature from about 20° C. to about 40° C., and whereinthe first partially cured mixture of the first viscosity comprisescovalently bonded cyclic aliphatic chemical groups and PHA oligomers andpolymers. In some embodiments, the B-stage prepreg of the secondviscosity is produced at a temperature from about 40° C. to about 145°C., wherein the B-stage prepreg of the second viscosity comprisescovalently bonded cyclic aliphatic chemical groups and PHA oligomers andpolymers. A composite article produced by the method is a printedcircuit board.

BRIEF DESCRIPTION OF THE FIGURES AND DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings andin the body of the specification. It is to be noted, however, that theappended and embedded drawings illustrate only typical embodiments ofthis disclosure and are therefore not to be considered limiting of itsscope, for the disclosure may admit to other equally effectiveembodiments.

FIG. 1 is a cross sectional view of a multilevel interconnect scheme foran IC according to one embodiment of the disclosure.

FIG. 2 is a flowchart depicting steps associated with an exemplarymethod 200 for application of a spin-on dielectric material according toone embodiment of the disclosure.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures and drawings. It is contemplated that elements disclosed inone embodiment may be beneficially utilized on other embodiments withoutspecific recitation.

DETAILED DESCRIPTION

To solve the RC delay issues in both ICs and PCBs, new low-k PHTmaterials and methods for their preparation are presented in thedisclosure, whereby cyclic aliphatic chemical groups enhance thephysical and electrical properties of the PHTs, and enable their use inelectronic applications. The overall dielectric constant of an articleor composite, comprising multiple materials or components, is theweighted sum of the dielectric constants of all the materials orcomponents that make up the article or composite. The dielectricconstant of an article, composite or bulk material is derived from thefrequency dependent sum total of the polarizability derived frommolecular structure, chemical groups and chemical bonds, which makeelectronic, ionic and polar contributions. In the case of aromatic PHTs,the electronic component or contribution to polarizability refers to theoscillation of electrons in the chemical bonds (both sigma and pi) inthe extended supramolecular structure. Therefore, in low-k materialdesign, it is desirable to minimize or eliminate ionic and polarcontributions, and polarizable pi electrons. One example of such a low-kmaterial suitable for electronic applications is a new low-k PHTcomprising cyclic aliphatic chemical groups that lack pi electrons.Advantageously, new cyclic aliphatic low-k PHTs may be produced withoutadditional solvent from commercially available reagents such ascycloaliphatic diamines such as 1,4-diaminocyclohexane (DCH) andparaformaldehyde (PF), as shown reaction example 1.

Reaction Example 1

Per reaction example 1, and in other embodiments, the amine(s) may serveas a reaction mixture solvent and/or a co-solvent, which may saveadditional steps involving solvent removal and disposal. Generalconditions for PHT formation, such as that shown in reaction example 1,involve combining PF and amines in a dry and degassed vessel, whereinthe PF and amines may be in a ratio of about 1.25 mole PF:0.5 moleamine. The well stirred reaction mixture may then be heated from about30° C. and about 50° C. to cause the reaction of the aliphatic aminewith PF, and thus produce a PHA material over a time period from about0.5 hours to about 2 hours. In some embodiments a PHT film may beproduced by casting or spin coating an aliquot of the reaction mixturesolution onto a substrate, followed by heating to about 200° C. forabout 1 hour, and then soaking the film at 200° C. for about 1 hour,followed by cooling to ˜23° C. Further details regarding PHT productionare provided later in the disclosure.

We note here that chemical reaction examples in the disclosure, such asreaction example 1, may have non-limiting symbols used in the chemicalarts such as chemical formulas, equations, a triangle under an arrowwhich serves an abbreviation to indicate a heating of the reactionmixture, and wavy or squiggly lines attached to an atom in a chemicalformula that represent a chemical bond between that atom and anotheratom or chemical structure not shown in the formula. Further, thechemical structure indicated by use of a wavy line may be a recurringchemical structure, such as a polymer, a quasi-recurring chemicalstructure, such as a polymer with varying monomer and bridge units, or anon-recurring chemical structure, such as a terminating group.

Those skilled in the art will appreciate that the cycloaliphaticdiamine, DCH, as shown in reaction example 1, is non-limiting componentin the preparation of low-k PHTs. In general, the practitioner maychoose any small molecule, oligomer, or polymer comprisingmultifunctional amines, aliphatic amines, cyclic amines and optionallysome mole fraction of aromatic amine(s) in a low-k PHT synthesis. Theamines may have mono, di, tri, tetra, or penta amine functionality. Thealiphatic amine may also have one or more aliphatic amine groups, whichmay be primary and/or secondary, or mixtures thereof. Aliphatic andaromatic ring structures comprising amine chemical groups may bemonocyclic or polycyclic, and may further comprise fused rings andpendant rings. “Fused rings” refers to two ring chemical structures thatshare at least two atoms. In other words, a ring structure A and a ringstructure B form a fused ring structure if A and B share at least twoatoms. The number of carbon atoms in the ring structures are notrestricted, but we note that carbon rings comprising less than 5 carbonatoms may be more prone to bond scission than ring structures with 5carbon atoms or more. For example, cyclobutane is more prone to thermalbond scission than cyclopentane. The cyclic chemical structures belowillustrate some possible positions of amine groups on aliphatic ringstructures. As shown below, a decalin molecule may have the ring carbonatoms numbered 1-10, and amine groups may be attached to at least one ofthese positions, for example, the diamine shown below, 5,10-diamino-decahydronaphthalene.

We note that the position of the amine group on the ring(s) (e.g., axialposition versus equatorial position), the ring(s) conformation, andresultant torsional strains and steric interactions may affect the bulkphysical properties of the PHT such as Tg, modulus and flexibility.Notably, by judicious choice of ring structure, amine group positions,and number of carbon atoms, the bulk polymer physical properties may bemodified as needed. Cyclic aliphatic amines and cyclic structures thatcomprise low-k PHTs may also provide a high modulus network without theinherent brittleness found in highly aromatic systems, and do notcontain lossy pi electrons which increase the dielectric constant.Further, cyclic aliphatic polymers, in comparison to linear polymers,have less bond rotation and thus are more rigid, and thus may featurehigher glass transition temperatures (Tg), increased thermal stability,and higher modulus, while still maintaining some flexibility.

In another embodiment, a low-k PHT comprising bulky polycyclic adamantylrings may be produced by reacting 1,3-adamantanediamine and it's isomerswith PF, as shown in reaction example 2:

Reaction Example 2

Advantageously, PHT networks containing adamantane ring structures andother ring structures such as norborane diamine ring structures, mayproduce PHT networks with greater free volume, which may result in alower dielectric constant. This is because the polycyclic ringstructures are bulky and take up space within a polymer network whererotational and translational movements are restricted. The largepolycyclic structures may also interrupt local and long range molecularpacking and crystallization, which may also create more network freevolume.

Generally, the cyclic aliphatic amine chemical group may be at least onecovalent ring structure or multiple covalent ring structures(polycyclic), and may further comprise of bridging groups, polymericsegments, and other chemical functionality, aromatic and/or aliphatic.In some embodiments, the low-k PHT network may contain a mole fractionof aromatic groups based on polymer, to increase the modulus andstiffness, but without increasing the overall k value significantly.More specifically, to maintain a dielectric constant of less than 5,less than 50% by mole aromatic structures based on polymer may beintroduced into the network, without raising the dielectric constant bymore than about 0.5 to about 1.0. In one embodiment, a illustrated byreaction example 3, a polycyclic diamine containing both aliphatic andaromatic structures is reacted with PF to produce a PHT network with anincreased modulus:

Reaction Example 3

In another embodiment, a PHT network comprising both aliphatic andaromatic ring structures may be produced with a mixture comprisingcyclic aliphatic diamines such as DCH and aromatic amines such as ODAwith PF. It is noted that those skilled in the art may use any number ofnon-limiting combinations of aliphatic and aromatic ring structures toproduce low-k PHTs. For example, polycyclic diamines such asadamantanediamine and norbornanediamine may also be combined witharomatic diamines such as ODA and paraphenylenediamine in properproportions as noted above, to produce low-k PHT's.

The practitioner may choose to reduce the polarizability of PHTs furtherby the use of covalently bonded fluorine atoms. For example, a PHTnetwork containing fluorine may be produced with an amine comprisingstructures and chemical groups that contain covalently bonded fluorineatoms. Advantageously, C—F bonds in a chemical structure may lower the kvalue of the molecule or polymer because C—F bonds have a lowerpolarizability than C—H bonds, and in aromatic structures, C—F bonds maylower the polarizability of pi electrons. Additionally, fluorinecontaining polymers repel high-k polar water molecules due to theirlower surface energies. One non-limiting example of a fluorinated PHT isillustrated in reaction example 4, wherein a fluorinated difunctionalamine is reacted with PF to produce a fluorinated low-k PHT with a kvalue that may be from about 2.5 to about 3.5.

Reaction Example 4

Generally, the PHA or PHT network may comprise of chemical functionalityand/or chemical groups that may engage in other chemical reactions,transformations, or interactions, before, during or after the formationof a PHT network or polymer, including, but not restricted to:synthesis, decomposition, single replacement and double replacement,oxidation/reduction, acid/base, nucleophilic, electrophilic and radicalsubstitutions, and addition/elimination reactions. In some embodiments,the cyclic segments that bridge hexahydrotriazine groups may engage inpolymerization reactions such as condensation, step growth, chain growthand addition polymerizations. In other embodiments, reactive chemicalgroups or other reactive matrix functionality may undergo furtherchemical reactions, as initiated by heat or light, or other means suchas nucleophilic or electrophilic attack, or by free radical mechanismsof bond formation. In one non-limiting example, residual double bonds inthe polymeric structure may be further reacted to create cross-linksusing free radical chemistry, such as that initiated by azo, inorganicand organic peroxides. In other embodiments, thermally inducedcyclization or rearrangement reactions may be used to form chemicalbonds and cross-links that may increase the modulus of the PHT network.In other embodiments some PHT matrix chemical groups may be more polarin nature, or may have a hydrophilic/lipophilic balance that is adjustedby the practitioner for certain properties, such as modulus, adhesivestrength, and control of water absorption for example. The pendant groupmay be a hydrogen bonding pendant group, such as hydroxyl, which mayengage in hydrogen bonding with a polar component in a compositematerial, such as reinforcing fiber or mineral filler. In someembodiments an interaction of this type may lead to increased adhesionof the PHT to a polar component and result in less cracking.

The following describes non-limiting chemical reaction conditions andprocedures for the preparation of low-k PHAs and PHTs comprisingcovalently bound cyclic aliphatic chemical groups:

(1) The solvent may be a multifunctional cyclic aliphatic amine or otheramines. Alternatively, a co-solvent may be used, including dipolaraprotic solvents such as, for example, N-methyl-2-pyrrolidone (NMP),dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMA), propylene carbonate (PC), and propyleneglycol methyl ether acetate (PGMEA).

(2) Under inert dry conditions, a reaction vessel containing PF may becharged with the amine(s), amine solvents, and/or co-solvent(s) in theappropriate stoichiometric ratio, so that the moles of PF are sufficientto form PHA/PHT hexahydrotriazine structures, such as a ratio 1.25 molePF to 0.5 mole amine. The reaction mixture may also comprise a mixtureof different aliphatic and/or aromatic amines for hexahydrotriazineformation, in some combination. For example, the mixture may contain twoamines, such as ODA (an aromatic bridging diamine) and the cyclicaliphatic difunctional amine, 1,4-diaminocyclohexane (DCH).Specifically, multifunctional amines may be used to create covalentlyPHA and PHT structures, but, if suitable or so desired, monoamines mayalso be used at some stoichiometric proportion. The well stirredreaction mixture may be then heated from about 30° C. and about 50° C.to cause the reaction of the amines with PF, and thus produce a PHAmaterial over a time period from about 0.5 hours to about 2 hours. Inanother embodiment, DCH and PF in the proper stoichiometric ratio arereacted for 1 hour at 50 C to create a mixture comprising PHA. In theseembodiments and others, the PF serves as a “thermal latent curingagent”, that is, it does not undergo reaction with the amines to formhexahydrotriazine structures until heated. In some embodiments thereaction mixture may be cooled, or quenched, so that a reaction mixtureof a desired viscosity is obtained and isolated, and wherein the mixturemay comprise of PHA oligomers, polymers, and unreacted PF. Such amixture may be suitable for coating substrates, followed by furtherheating to produce a desired state of cure.

In other embodiments the PHA material may not be isolated, and a PHTproduct may be formed directly, wherein the reaction mixture may heatedfrom about 190° C. to about 210° C. for a period of time of about 1minute to about 24 hours, and more preferably about 1 hour. In onenon-limiting example a PHT thin film may be isolated by depositing analiquot of the reaction mixture solution onto a substrate, such as aglass microscope slide with aluminum tape (80 μm thickness) boundariesusing a glass Pasteur pipette. The following thermal treatment may beused to drive off non-reactive co-solvent and cure the film: a) 50° C.for about 1 hour, b) 50° C. to 110° C. for about 1 hour, c) 110° C. forabout 1 hour, d) 110° C. to 200° C. for about 1 hour, and then 200° C.for about 1 hour, followed by cooling to ˜23° C. In another embodiment,the thermal treatment may be as follows: a) 50° C. for about 1 hour, b)50° C. to 200° C. over a time period of about 1 hour, c) 200° C. forabout 1 hour, followed by cooling to ˜23° C.

In one embodiment the reaction mixture may be used as a spin-oninterlevel dielectric used in ICs, as illustrated in cross-section inFIG. 1, showing a dielectric between metal lines and vias in a 4 levelwiring scheme. FIG. 2 is a flowchart depicting steps associated with amethod 200 used to form a dielectric film on a silicon wafer substrate,and to ultimately produce a structure like that shown in FIG. 1. At 201,a patterned silicon wafer comprising a plurality of electrical circuitryand components used to create a plurality of ICs is affixed to a spincoater chuck. Then, at 202, the wafer may be cleaned to remove dust,particulates and other contaminants using ultra pure inert gas and/orappropriate solvents. At 203, a reaction mixture of a first viscositythat may comprise of combinations of monomers, solvent, oligomers andpolymers of PHA, is dispensed and thus applied to the center of thewafer. It is further noted that those skilled in the art may produce areaction mixture of a first viscosity by heat treatment of the reactionmixture as described prior, such as a well stirred reaction mixture thatis heated from about 30° C. and to about 60° C., so as to cause thereaction of amine(s) with PF, and thus produce a PHA material over atime period from about 0.5 hours to about 2 hours. At 204 the mixture isspread, or spun over and upon the substrate at a first RPM, and at 205,the mixture is further spread or spun over the substrate at a secondRPM, or a schedule of increasing RPM values to create a first filmthickness. At 206, an edge bead may be removed and the wafer backsidemay be cleaned using an appropriate solvent. 207 involves heating thesubstrate on a hot plate or another appropriate heated surface to removesolvents and/or co-solvents. At 208, a soft cure is performed whereinmore PHA extended structure is produced within the film and the PHAformation is substantially completed, such as about 75% percent to about100% completion. At this juncture, the wafer may be handled if sodesired, as the film viscosity has been increased so that the film is ina near solid state or a solid state and thus will not run easily. At209, an additional coat may be applied as needed to build the filmthickness further, and 209 may be repeated as deemed necessary to createa final thickness, in conjunction with steps 207 and 208. Finally, at210, the substrate comprising a final thickness of PHA is heated per thefollowing schedule to produce a PHT film: a) 110° C. to about 200° C.for about 1 hour, and then 200° C. for about 1 hour, followed by coolingto ˜23° C. We note that the above Method 200 is a non-limiting exampleof a method used to produce a low-k PHT interlevel dielectric thin filmon a substrate or wafer.

A composite article such as a PCB dielectric substrate may also beproduced using the aforementioned reaction mixture. Here, a firstviscosity mixture is produced by heat treatment of the reaction mixtureas described prior, such as a well stirred reaction mixture that isheated from about 30° C. and to about 60° C., so to cause the reactionof the amine(s) with PF, and thus produce a mixture comprising PHAoligomers and polymers over a time period from about 0.5 hours to about2 hours, and so that a desired working viscosity is obtained. Themixture may be then applied to a fiber mat or matrix, such as thatproduced from fiberglass or carbon fiber, and thus impregnating thefiber mat with the partially cured mixture. The fiberglass mat thusobtained may be known as a polymer pre-impregnated mat (pre-preg). Atthis juncture, excess partially cured resin and other components may beremoved from the prepreg by a squeegee, and then the prepreg may besubjected to further heat to achieve a certain desired stage of cure,followed by cooling to stop the chemical reaction(s), and so that thematerial may be handled. This composite precursor article may be termeda “B-stage” prepreg, wherein the resin mixture is partially cured,maintains some flexibility, and may be handled for further transport ofprocessing. The B-stage prepreg may comprise of PF, PHA oligomers andpolymers and other reaction components. At this stage the B-stageprepreg may be used to create a composite article in a mold. The articlemay be produced by further heating to about 200° C. in a vacuumautoclave to complete the reaction of the amine components with thethermal latent PF in the mixture, remove solvent, and thus produce acomposite with PHT matrix resin.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention. Asused herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” when used in this specification, specify thepresence of stated features, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, elements,components, and/or groups thereof. When a range is used to express apossible value using two numerical limits X and Y (e.g., a concentrationof X ppm to Y ppm), unless otherwise stated the value can be X, Y, orany number between X and Y.

The description of the present invention has been presented for purposesof illustration and description, but is not intended to be exhaustive orlimited to the invention in the form disclosed. Many modifications andvariations will be apparent to those of ordinary skill in the artwithout departing from the scope and spirit of the invention. Theembodiments were chosen and described in order to best explain theprinciples of the invention and their practical application, and toenable others of ordinary skill in the art to understand the invention.

What is claimed is:
 1. A polyhexahydrotriazine (PHT), comprising: aplurality of trivalent hexahydrotriazine groups having the structure

and a plurality of carbon groups having the structure

wherein each wavy bond site of a given hexahydrotriazine group iscovalently linked at a respective wavy bond site of a carbon group, andeach wavy bond site of a given carbon group is covalently linked at arespective wavy bond site of a hexahydrotriazine group, and wherein atleast one of 1, 2, and 3 comprises a chemical group that is a cycliccarbon chemical group, or 1 and 2 are part of a polycyclic hydrocarbonchemical group, or 2 and 3 are part of a polycyclic hydrocarbon chemicalgroup, or 1 and 3 are part of a polycyclic hydrocarbon chemical group.2. The PHT of claim 1, wherein at least one of 1, 2, and 3 is acovalently bonded carbon substituent.
 3. The PHT of claim 2, wherein atleast one of 1, 2, and 3 comprises a covalently bonded cyclic aliphaticchemical group.
 4. The PHT of claim 3, wherein at least one cyclicaliphatic chemical group comprises at least one cyclic carbon ring. 5.The PHT of claim 4, wherein at least one cyclic carbon ring is fused toat least one other cyclic carbon ring.
 6. The PHT of claim 1, wherein atleast one of 1, 2, and 3 covalently bonds at least one hexahydrotriazinegroup to another hexahydrotriazine group.
 7. A polyhexahydrotriazine(PHT), comprising: a plurality of trivalent hexahydrotriazine groupshaving the structure

and a plurality of carbon groups having the structure

wherein each wavy bond site of a given hexahydrotriazine group iscovalently linked at a respective wavy bond site of a carbon group, andeach wavy bond site of a given carbon group is covalently linked at arespective wavy bond site of a hexahydrotriazine group, and wherein atleast one of 1, 2, and 3 comprises a chemical group that is a cycliccarbon chemical group, or 1 and 2 are part of a cyclic carbon chemicalgroup, or 2 and 3 are part of a cyclic carbon chemical group, or 1 and 3are part of a cyclic carbon chemical group, and the PHT furthercomprises at least 50% by mole aliphatic carbon-carbon chemical bondsbased on polymer.
 8. The PHT of claim 7, comprising at least 50% by molecyclic aliphatic carbon-carbon chemical bonds based on polymer.
 9. ThePHT of claim 8, comprising less than 50% by mole aromatic carbon-carbonchemical bonds based on polymer.
 10. A polyhexahydrotriazine (PHT),comprising: a plurality of trivalent hexahydrotriazine groups having thestructure

and a plurality of carbon groups having the structure

wherein each wavy bond site of a given hexahydrotriazine group iscovalently linked at a respective wavy bond site of a carbon group, andeach wavy bond site of a given carbon group is covalently linked at arespective wavy bond site of a hexahydrotriazine group, and wherein atleast one of 1, 2, and 3 comprises a chemical group that is a cycliccarbon chemical group, or 1 and 2 are part of a cyclic carbon chemicalgroup, or 2 and 3 are part of a cyclic carbon chemical group, or 1 and 3are part of a cyclic carbon chemical group, and the PHT furthercomprises covalently bonded fluorine atoms.
 11. The PHT of claim 10,comprising cyclic chemical groups that contain covalently bondedfluorine atoms.
 12. The PHT of claim 1, wherein the PHT has a dielectricconstant less than
 5. 13. The PHT of claim 12, wherein the PHT has adielectric constant of at least 1.8.
 14. The PHT of claim 1, wherein 1and 2 are part of a polycyclic hydrocarbon chemical group, or 2 and 3are part of a polycyclic hydrocarbon chemical group, or 1 and 3 are partof a polycyclic hydrocarbon chemical group, and at least one polycyclichydrocarbon chemical group includes a fused ring structure.
 15. The PHTof claim 14, wherein at least one polycyclic hydrocarbon chemical groupincludes a cyclic aliphatic chemical group.
 16. The PHT of claim 14,wherein at least one polycyclic hydrocarbon chemical group includes acyclic aromatic chemical group.
 17. The PHT of claim 14, comprisingcovalently bonded fluorine atoms.
 18. The PHT of claim 17, wherein atleast one polycyclic hydrocarbon chemical group contains covalentlybonded fluorine atoms.
 19. The PHT of claim 14, wherein the PHT has adielectric constant less than
 5. 20. The PHT of claim 19, wherein thePHT has a dielectric constant that is at least 1.8.